Production of uniform droplets using membrane, microchannel and microfluidic emulsification devices

This review provides an overview of major microengineering emulsification techniques for production of monodispersed droplets. The main emphasis has been put on membrane emulsification using Shirasu Porous Glass and microsieve membrane, microchannel emulsification using grooved-type and straight-through microchannel plates, microfluidic junctions and flow focusing microfluidic devices. Microfabrication methods for production of planar and 3D poly(dimethylsiloxane) devices, glass capillary microfluidic devices and single-crystal silicon microchannel array devices have been described including soft lithography, glass capillary pulling and microforging, hot embossing, anisotropic wet etching and deep reactive ion etching. In addition, fabrication methods for SPG and microseive membranes have been outlined, such as spinodal decomposition, reactive ion etching and ultraviolet LIGA (Lithography, Electroplating, and Moulding) process. The most widespread application of micromachined emulsification devices is in the synthesis of monodispersed particles and vesicles, such as polymeric particles, microgels, solid lipid particles, Janus particles, and functional vesicles (liposomes, polymersomes and colloidosomes). Glass capillary microfluidic devices are very suitable for production of core/shell drops of controllable shell thickness and multiple emulsions containing a controlled number of inner droplets and/or inner droplets of two or more distinct phases. Microchannel emulsification is a very promising technique for production of monodispersed droplets with droplet throughputs of up to 100?l?h^?1.     

Ion exchange of intercalation compounds from WOP2O7 and intercalation ofn-alkylamines

Ion exchange of Na _x WOP₂O₇ ·nH₂O (x 1.4) prepared from WOP₂O₇ was attempted, using alkaline and alkaline earth ions. The degree of exchange was observed to be >50% at 90° C except for Mg²⁺. The basal spacing of ion-exchanged materials for the hydrated phase were dependent on the number of water molecules in the interlayer spaces, while those for the dehydrated phase increased with the size of ions in the interlayer spaces. The network of water molecules linked by the hydrogen bond in the interlayer spaces seems to determine the basal spacing. By the ion-exchange reaction,n-alkylammonium ions were intercalated into the interlayer spaces of Na _x WOP₂O₇ ·nH₂O (x 1.4) and Sn _x H _y WOP₂O₇ ·nH₂O (2x +y 0.5). In spite of the difference in the charge density of the host layer, a similar arrangement of alkyl chains in the interlayer spaces resulted, and neutral amines were considered to be intercalated as well as ammonium ions. Direct reaction ofn-alkylamine with WOP₂O₇ produced an intercalation compound without reduction of tungsten. The arrangement of the amines in the interlayer spaces is similar to that supposed to the ion-exchanged derivatives when heated at 140° Cin vacuo.     

Polymerization via zwitterion 25. Alternating copolymerizations of cyclic acyl phosphorite and phosphite with vinyl monomers having an electron withdrawing group

Summary Spontaneous copolymerizations of cyclic acyl phosphonite (SPO) and phosphite (SPI) with an electron-deficient vinyl monomer such as methyl acrylate (MA), methyl vinyl ketone (MVK), and acrolein (AL), gave the corresponding alternating copolymers. These copolymerizations took place without added initiator and proceeded through zwitterion intermediates. Copolymer structures 1a, 1b, 2 and 3 have been established, all of which were derived in a regiospecific manner of ambident anions. The scheme of the copolymerizations is presented.     

Cationic ring-opening polymerization of 2-phenyl-1,3,6,2-trioxaphosphocane

Summary The ring-opening polymerization of 2-phenyl-1,3,-6,2-trioxaphosphocane (4), an eight-membered cyclic phosphonite, has been investigated. Cationic initiators of PhCH₂-Cl and MeOTf gave polymers, whereas anionic and radical initiators did not yield polymer. The structure of polymer was examined by IR, ¹H, ³¹P, and ³¹C NMR spectroscopy of polymers and elemental analysis as well as the alkaline hydrolysis products. The polymer consisted of two different units, i.e., the major part is the normal phosphinate structure 5 and the minor part is the isomerized unit 6 in 7% with PhCH₂Cl initiation and in 34% with MeOTf initiator. The difference in nature of propagating species from these two initiators are discussed in connection with their reactivities.On leave from the Institute of Chemistry, Academia Sinica, Beijing, China     

Cationic ring-opening polymerization of 2-phenyl-1,2-oxaphospholane (deoxophostone)

Summary The ring-opening polymerization of deoxophostone 5, a five-membered cyclic phosphinite, has been studied. Some cationic initiators gave polymer whereas anionic and radical initiators as well as metal chloride (Lewis acid) catalysts did not yield polymer. The polymer consisted of a phosphine oxide repeating unit 6. The polymerization proceeded via the Arbuzov-type reaction. The reduction of polymer 6 with a HSiCl₃/Et₃N system gave polyphosphine 7.     

Synthesis of silver/polymer colloidal composites from surface-functional porous polymer microspheres

This study presents a different colloidal silver (Ag)/polymer system where Ag nanoparticles are deposited uniformly onto surface-functional porous poly(ethylene glycol dimethacrylate-co-acrylonitrile) (poly(EGDMA-co-AN)) microspheres. The formation and morphology of the composite microspheres were characterized from electron microscopy and X-ray diffraction analyses. The significance of the present report is that owing to the high affinity between Ag and nitrile group (CN) on the large surface of the microspheres, the Ag nanoparticles having a face-centered cubic phase were incorporated evenly into the deep pores of the microspheres with fine size and size distribution. In the preservation test, the Ag/poly(EGDMA-co-AN) composite microspheres obtained showed an excellent anti-bacterial performance, elucidating a high applicability for a new preservative.     

Dynamics of the wet-end section in paper mills

A model representing the wet-end section of a paper mill has been developed to characterize its dynamic behavior during the grade change. The model is based on the mass balance relationships written for the simplified wetend white water network. From the linearization of the dynamic model, higher-order Laplace transfer functions were obtained followed by the reduction procedure to give simple lower-order models in the form of 1^st-order or 2^nd-order plus dead times. The dynamic response of the wet-end is influenced both by the white water volume and by the level of wire retention. Effects of key manipulated variables such as the thick stock flow rate, the ash flow rate and the retention aid flow rate on the major controlled variables were analyzed by numerical simulations. The simple dynamic model developed in the present study can be effectively used in the operation and control. This paper is dedicated to Professor Se Ki Moon on the occasion of his retirement from Hanyang University.     

Influence of Metal Ions on the Order-Disorder Transition Temperature of the Ba-M-O (M: La, Y, In, or Ga) System

Preparation of BaLa₂O₄, B_a3,Y₄O₉, B_a,In₂O₅, and Ba₃Ga₂O₆ powders and their sintering were investigated in Ar or air. These sintered bodies with perovskite-related structure were synthesized by reaction sintering, using mixed powders in the atomic ratios of Ba/La = 1, Ba/Y = 0.75, Ba/In = 1, and Ba/Ga = 1.5. The order-disorder transition temperatures of the BaLa₂O₄, Ba₃Y₄O₉, Ba₂In₂O₅, and Ba₃Ga₂O₆ sintered bodies were 270°, 350°, 880°, and 123O^oC, respectively. It was found that the temperatures were influenced by the ionic radius of cations in B sites, and the transition temperatures decreased with increasing ionic radius.     

Effects of functional groups in glow discharge polymerization

Summary Glow discharge polymerizations of allyltrimethylsilane (ATMS) and trimethylvinyloxysilane (TMVOS) were investigated by elemental analysis and infrared spectroscopy. The formed polymers were far different in elemental composition from the starting materials, and possessed high carbon and hydrogen contents. There was less difference in an infrared-spectral sense between the two polymers from ATMS and TMVOS. A polymer-forming process in a discharge state is discussed.